Process for the production of living (co)polymers and use of the (co)polymers

ABSTRACT

The purpose of the present invention is to provide polymerization catalyst which can produce quite efficiently (co)polymer having number average molecular weight and number of molecules which are accurately controlled in producing method of (co)polymer by the polymerization of polar unsaturated compound, and provide living polymerized (co)polymer obtained according to the producing method. For the purpose, polymerization catalyst composition which comprises the composition comprising organic oxysalt compound and hydroxycarbonyl compound having at least both an alcoholic hydroxyl group and a carbonyl group in the same molecule is provided and the polar unsaturated compound is polymerized by using the polymerization catalyst composition. The composition containing the obtained (co)polymer were able to provide thermosetting powder coating composition having particularly excellent characteristics.

TECHNICAL FIELD

The invention described herein relates to a method of producing a livingpolymerized (co)polymer by polymerizing a polar unsaturated compoundusing an organic oxysalt compound as catalyst. These polymer andcopolymer are very important ones as raw materials of polymer materialsand functional polymers.

The invention relates particularly to compositions of thermosettingpowder coatings, more particularly, to the compositions of thermosettingpowder coatings having excellent storage stability (blockingresistance), external appearance (surface flatness, brightness, andtransparency), physical property (hardness, scratch resistance, andrecoating property), and chemical property (weather resistance, acidresistance, and solvent resistance) and to the compositions ofthermosetting powder coatings which can provide baked coating filmsparticularly suitable for use of coating vehicles.

BACKGROUND ART

Enormous number of researches have been made with regard to thepolymerization of polar unsaturated compounds for many years. Amongthem, recently a number of researches on living polymerization catalystshave been conducted aiming at producing polymers having less narrowmolecular weight distribution by controlling optionally and rigorouslythe molecular weight of polymers to be obtained and variouspolymerization catalyst systems have been developed which have theproperty of living radical polymerization, living anion or livingcoordination anion polymerization (for example, living radicalpolymerization catalysts: Koubunshi, vol.48, (7) pp 498-501 (1999);living anion and living coordination anion polymerization catalysts:Shin koubunshi Jikkengaku vol.2“Shin Koubunshi noGousei•Hannou(1)—Fukakei koubunshi no Gousei—” pp 165-196, KyourituShuppan Kabushikigaisha (1995)).

Many effective living polymerization catalysts have been developed andfrom the view point of “the number of produced polymer moleculescorresponding to the number of molecules of polymerization catalystused” in most cases only one polymer molecule is obtained from onemolecule of polymerization catalyst, that is, stoichiometricpolymerization is observed. This stoichiometric living polymerizationrequires one molecule of the polymerization catalyst to produce onepolymer molecule which is not an efficient and effective method ofproduction in the light of industrially practical use. On the otherhand, in catalytic living polymerization wherein plural number ofpolymer molecules are produced by one molecule of polymerizationcatalyst it is possible to avoid or simplify the complicated processesof separating catalysts and control unfavorable effects on the polymerproperty to a minimum by reducing drastically the concentration ofcatalyst components remaining in the polymer produced. Furthermore, thismethod is a really practical one from the view point of reducingenvironmental load and catalyst cost. Actually, the polymerizationcatalyst systems of polar unsaturated compounds which have beenpracticed are composed of very small amount of radical generating agents(which mean the catalysts described herein) and a large amount of chaintransfer agents. Although the polymerization does not proceed likeliving one, it produces very efficiently the number of polymer moleculescomparable to the number of molecules of the chain transfer agents fromone radical molecule.

The known examples of the catalytic living polymerization of polarunsaturated compounds are {circumflex over (1)} polymerization ofmethacrylate using alkali metal alkoxide as catalyst and alcohol aschain transfer agent (S. N. Lewis et al., Progress in Organic Coating12, 1-26 (1984)) and {circumflex over (2)} polymerization ofmethacrylate and acrylate using quaternary ammonium salt or Lewis acidas catalyst and silyl ketene ketal as chain transfer agent (O. W.Webster et al., J.Am.Chem.Soc., 105, 5703 (1983) or Shin koubunshiJikkengaku vol.2“Shin Koubunshi no Gousei•Hannou(1)—Fukakei koubunshi noGousei—” pp 365-386, Kyouritu Shuppan Kabushikigaisha (1995)). However,the method {circumflex over (1)} is a good polymerization method forproducing oligomers having average molecular weight of 500-3000 butcannot produce oligomers having average molecular weight greater than orequal to 3000 or (co)polymers by controlling their molecular weight andmolecular weight distribution precisely. Furthermore, since this methoduses alcohol as both chain transfer agent and polymerization solvent,transesterification proceeds simultaneously with polymerization.Therefore, there is a drawback that this method cannot apply to themonomers when the transesterification causes some problems. The method{circumflex over (2)} has not been practiced yet, because silyl keteneketal is expensive and unstable and there are some problems in theproduction method.

As an important use utilizing the property of the (co)polymer which isobtained by the method of the present invention there are powdercoatings and prior arts relating to them which will be explained in thefollowing:

Solvent type coating materials have usually been used for paintingbodies and those which satisfy various requirements have been developedand used in order to be utilized in the field of automobiles whererigorous quality specification is required.

Recently in the technical field of coating materials, shift to usingpowder coatings have been expected in place of solvent type coatingmaterials in the light of local or global environment conservation,environment improvement of health and safety at work, prevention of fireand explosion, and resource conservation. And from the historical andsocial requests, as expectation for high function performance anddiversification of powder coatings have been increased, high paint filmperformance (for example, weather resistance, acid rain resistance, andscratch resistance) of powder coatings comparable to solvent typecoating materials have been requested. However, in spite of severerequests for paint film performance, powder coatings which satisfy theserequests have not necessarily been placed on the market.

As specific examples of the conventional types of powder coatings thereare those of epoxy resin and polyester resin. However, these coatingshave not only problems in weather resistance but also in resistanceagainst the acid rain which has recently become a particular problemand, therefore, these problems were regarded as critical in the field ofpainting automobile bodies.

For the purpose of eliminating the drawback, acrylic powder coatings wasproposed in JP-B-48-38617 and remarkable improvement in weatherresistance has been realized. Since then many researches have been madeon the acrylic powder coatings, however, these acrylic powder coatingshave not satisfied sufficiently external appearance property, physicalproperty, chemical property, storage property, and particularly surfaceflatness and blocking resistance simultaneously. Reduction in meltviscosity is the most effective to improve the surface flatness,however, in order to reduce the melt viscosity it was necessary to lowera glass transition temperature by which method it was impossible tosatisfy both the surface flatness and the blocking resistance.

For the purpose of providing the surface flatness and the blockingresistance simultaneously, thermosetting powder coatings composition(WO96/03464) is proposed which uses acrylic (co)polymer having narrowmolecular weight distribution. It is surely possible to have the surfaceflatness and the blocking resistance simultaneously by narrowing themolecular weight distribution. However, according to the method ofliving polymerization which is described as an example of producingmethod of the acrylic (co)polymer used therein, due to the insufficientrecoating property (adhesion property with top coatings at repaintingand maintenance) the powder coatings, particularly as top coatings, didnot show the effectiveness sufficiently. As another example of theproduction, an acrylic (co)polymer having the prescribed molecularweight distribution is shown by fractionating the acrylic (co)polymerobtained by radical polymerization method. However, in this method theproportion of the (co)polymer to be obtained as a target is low and aprocess of the fractionation is required, therefore, the method iscostly and not practical. Researches on various living polymerizationmethods have been conducted for the purpose of narrowing the molecularweight distribution of acrylic (co)polymer, however, because ofcoloring, stench, and high cost of the acrylic (co)polymers producedthere have not been the method of producing acrylic (co)polymers andthermosetting powder coatings which can favorably be applied to paintingautomobile bodies and parts for vehicles such as automobiles,particularly, painting of top coatings.

The purpose of the present invention is to provide a method of producingliving (co)polymers effectively and efficiently by catalytic livingpolymerization of polar unsaturated compounds when (co)polymers areproduced by the polymerization of polar unsaturated compounds.

Another purpose of the present invention is to provide thermosettingpowder coating compositions (for example acrylic thermosetting powdercoating compositions) having storage stability, external appearanceproperty, physical property, and chemical property in the light of theproblems described above; particularly to provide thermosetting powdercoating compositions (for example acrylic thermosetting powder coatingcompositions) which are applied favorably to the painting automobilebodies and parts for vehicles such as automobiles (aluminum wheels,windshield wipers, pillars, door handles, fenders, bonnets, airspoilers, stabilizers, and front grilles), particularly, to the paintingof top coatings.

DISCLOSURE OF THE INVENTION

As a result of the extensive and through researches to achieve thepurposes described above, the inventors of the present invention havecompleted the present invention by finding out that by a method ofpolymerization of polar unsaturated compounds using an organic oxysaltcompound as catalyst in the presence of a hydroxycarbonyl compoundhaving at least both an alcoholic hydroxyl group and a carbonyl group inthe same molecule the polymerization has the property of stoichiometricor catalytic living polymerization and it is possible to controlprecisely not only the average molecular weight of the (co)polymerproduced but also the number of the molecules of the (co)polymer.

That is, the present invention is a method of producing a livingpolymerized (co)polymer comprising polymerization of polar unsaturatedcompound using organic oxysalt compound as catalyst in the presence of ahydroxycarbonyl compound having at least both an alcoholic hydroxylgroup and a carbonyl group in the same molecule when producing the(co)polymer by (co)polymerization of polar unsaturated compounds usingoxysalt compound as catalyst.

Furthermore, as a result of more extensive and through researches toresolve the problems of the prior arts as described above, the inventorsfound out the knowledge that by using the (co)polymer(A) as describedabove it is possible to provide a thermosetting powder coatingcomposition having excellent storage stability, external appearance,physical property, and chemical property (for example, an acrylicthermosetting powder coating composition) and completed the presentinvention.

The present invention is specified by items as described in thefollowing [1]-[17]:

[1] A method of producing a living polymerized (co)polymer which methodcomprises polymerization of polar unsaturated compound in the presenceof a hydroxycarbonyl compound having at least both an alcoholic hydroxylgroup and a carbonyl group in the same molecule using an organic oxysaltcompound as catalyst.

[2] The method as described in [1], wherein a cation forming the organicoxysalt compound is an alkali metal cation, a tetraalkylammonium cation,a trialkylsulfonium cation, a tetraarylphosphonium cation, ahexaarylphosphoranilidene ammonium cation, or atetrakis{tris(dialkylamino)phosphoranilideneamino}phosp honium cation.

[3] The method as described in [1], wherein the cation forming theorganic oxysalt compound is a tetraalkylammonium cation, atetraarylphosphonium cation, or a hexaarylphosphoranilidene ammoniumcation.

[4] The method as described in any one of [1] to [3], wherein an anionforming the organic oxysalt compound is an organic oxyanion derived froma monohydric alcohol, an organic oxyanion derived from amonocarboxylate, or an organic oxyanion derived from a polycarboxylate.

[5] The method as described in any one of [1] to [3], wherein an anionforming the organic oxysalt compound is an organic oxyanion derived froma monohydric alcohol.

[6] The method as described in any one of [1] to [5], wherein thehydroxycarbonyl compound is an α-hydroxyketone or anα-hydroxycarboxylate.

[7] The method as described in any one of [1] to [6], wherein the polarunsaturated compound is a chemical compound having both a polarfunctional group selected from carbonyl, cyano, or pyridyl groups, andan unsaturated group in the same molecule and, in addition, thefunctional group and the unsaturated group form a direct or indirectconjugated system.

[8]

The method as described in any one of [1] to [6], wherein the polarunsaturated compound is a (meth)acrylate, a (meth)acrylonitrile, a(meth)acrylamide, a vinylpyridine, a N-substituted maleimide, avinylketone, or a styrene derivative.

[9] The method as described in any one of [1] to [6], wherein the polarunsaturated compound is a monoester between a monohydric alcohol andacrylic acid or methacrylic acid, a monoester between acrylic acid ormethacrylic acid and a dihydric alcohol one end of which is protected byether linkage, a polyester formed by esterification between acrylic acidor methacrylic acid and all of the hydroxyl groups of the polyhydricalcohol, having two or more hydroxyl groups, an acrylonitrile, amethacrylonitrile, a N,N-disubstituted mono(meth)acrylamide, a pyridinesubstituted by vinyl or isopropenyl group, a N-aromatic substitutedmaleimide or a vinylketone.

[10] The method as described in any one of [1] to [9], wherein an activehydrogen compound is used as chain transfer agent.

[11] The method as described in any one of [1] to [9], wherein the chaintransfer agent is a , monocarboxylate, a polycarboxylate, a monohydricalcohol, a polyhydric alcohol, a monothiol, a (co)poly(alkyleneoxide)having an active hydrogen at its end and/or in its backbone chain, a(co)poly{(meth)acrylate)}, a (co)poly{(meth)acrylonitrile)}, a(co)poly{(meth)acrylamide}, a (co)poly(vinylpyridine), a(co)poly(N-substituted maleimide), a (co)poly(vinylketone), or a(co)poly(styrene derivative).

[12] The method as described in any one of [1] to [11], wherein thecopolymer is produced by using at least two or more of the polarunsaturated compounds together.

[13] A thermosetting powder coating composition comprising;

a living polymerized (co)polymer (A) obtained by the method as describedin any one of [1] to [12] and

a curing agent composition component(B) which can cure said (co)polymer.

[14] The thermosetting powder coating composition as described in [13],wherein the (co)polymer(A) comprises an epoxy group.

[15] The thermosetting powder coating composition as described in [13]or [14], wherein the (co)polymer(A) has a glass transition temperatureof 10° C.-100° C.

[16] The thermosetting powder coating composition as described in anyone of [13] or [15], wherein the curing agent composition component(B)which can cure the (co)polymer comprising;

(b-1) a polycarboxylic acid and/or

(b-2) a polycarboxylic acid anhydride.

[17] The thermosetting powder coating composition as described in anyone of [13] to [16] wherein the thermosetting powder coating compositionis for use as top coating of automobiles.

BEST MODES FOR CARRYING OUT THE INVENTION

The present invention relates to a method of producing a livingpolymerized (co)polymer by the (co)polymerization of a polar unsaturatedcompound using organic oxysalt compound as catalyst in the presence ofhydroxycarbonyl compound having at least both an alcoholic hydroxylgroup and a carbonyl group in the same molecule.

The organic oxysalt compound used in the present invention is a saltcompound composed of an anion part having univalent organic oxyanionstructure expressed by the formation of bonding an organic group to anoxygen atom as total structure or partial one and a cation part which isformed by a metal cation or an organic cation which can neutralize theanion in terms of electric charge.

As metal cations among the ones forming these organic oxysalt compoundsany metal cations may be used as far as they do not hinder the purposesof the present invention, and as specific examples of such cations,there are cations of alkali metals or those of alkaline earth metals. Asorganic cations any cations may be used as far as they do not hinder thepurposes of the present invention and as specific examples of suchcations, there are quaternary ammonium cations, tertiary sulfoniumcations, quaternary phosphonium cations, phosphoranilidene ammoniumcations, or phosphoranilideneaminophosphonium cations.

As quaternary ammonium cations among these organic cations, there are,for example, ammonium ions which have nitrogen atom bonding to fourhydrocarbon groups such as tetramethylammonium ion, tetraethylammoniumion, tetrabutylammonium ion, tetrahexylammonium ion,tricyclohexylmethylammonium ion, N,N-dimethylpiperidinium ion, ortrimethylphenylammonium ion, or nitrogenous heterocyclic ammonium ionssuch as N-methylpyridinium ion, N-tert-butylpyridinium ion,N-methylpyrrolidinium ion, N,N′-dimethylimidazolinium ion, orN,N′-diisopropylimidazolinium ion.

As tertiary sulfonium cations there are, for example, trimethylsulfoniumcation, triethylsulfonium cation, triisopropylsulfonium cation,tributylsulfonium cation, or phenyldimethylsulfonium cation.

As quaternary phosphonium cations, there are, for example,tetramethylphosphonium cation, tetraethylphosphonium cation,tetrabutylphosphonium cation, tetrahexylphosphonium cation,tetracyclohexylphosphonium cation, tetraphenylphosphonium cation,tetramethoxyphenylphosphonium cation, tetranaphthylphosphonium cation.

As phosphoranilidene ammonium cations, there are, for example,hexamethylphosphoranilidene ammonium cation, hexaethylphosphoranilideneammonium cation, hexapropylphosphoranilidene ammonium cation,hexabutylphosphoranilidene ammonium cation, hexaphenylphosphoranilideneammonium cation, or hexanaphthylphosphoranilidene ammonium cation.

As phosphoranilideneaminophosphonium cations, there are, for example,

tris(dimethylamino){tris(dimethylamino)phosphoranilideneamino}phosphonium cation,

tris(diethylamino){tris(diethylamino)phosphoranilidenea mino}phosphoniumcation,

bis(dimethylamino)bis{tris(dimethylamino)phosphoranilideneamino}phosphonium cation,

dimethylaminotris{tris(dimethylamino)phosphoranilidenea mino}phosphoniumcation,

tetrakis{tris(dimethylamino)phosphoranilideneamino}phos phonium cation,

tetrakis{tris(morpholino)phosphoranilideneamino}phospho nium cation, or

tetrakis{tris(piperazino)phosphoranilideneamino}phospho nium cation.

Among cations which form the organic oxysalt compounds, preferable onesare, for example, alkali metal cations such as lithium cation, sodiumcation, potassium cation, cesium cation, or rubidium cation, andtetraalkylanunonium ions such as tetramethylammonium ion,tetraethylaxmnonium ion, tetrabutylammonium ion, or tetrahexylammoniumion, and trialkylsuiphonium cations such as trimethylsuiphonium cation,triethylsuiphoniurn cation, triisopropylsulphonium cation, ortributylsuiphonium cation, and tetraarylphosphonium cations such astetraphenyiphosphonium cation, tetramethoxyphenyiphosphonium cation, ortetranaphthylphosphonium cation, and hexaarylphosphoranilidene ainmoniumcations such as hexaphenyiphosphoranilidene ammonium cation orhexanaphthylphosphoranilidene ammonium cation, ortetrakis{tris(dialkylamino)phosphoranhideneamino)}phosphonium cationssuch as tetrakis{tris(dimethylamino)phosphoranhideneamino}phosphoniumcation, tetrakis{tris(morpholino)phosphoranilideneamino}phosphoniumcation, or tetrakis{tris(piperazino)phosphoranilideneamino}phosphoniumcation; and more preferable cations are tetraslkylammonium cations,tetrasryiphosphonium cations, or hexasryiphosphoranilidene ammoniumcations.

On the other hand, as anions which form the organic oxysalt compounds inthe present invention, any organic anions may be used as far as they donot hinder the purpose of the invention. As specific examples, there areorganic oxyanions of monohydric alcohols which are derived by leavingactive hydrogen atoms as protons on the alcoholic hydroxyl groups, forexample, methanol, ethanol, n-propanol, isopropanol, n-butyl alcohol,sec-butyl alcohol, tert-butyl alcohol, isopentyl alcohol, tert-pentylalcohol, n-octyl alcohol, lauryl alcohol, cetyl alcohol, cyclopentanol,cyclohexanol, allyl alcohol, crotyl alcohol, methylvinylcarbinol, benzylalcohol, 1-phenylethyl alcohol, triphenylcarbinol, cinnamyl alcohol, orperfluoro-tert-butyl alcohol, and organic oxyanions of polyhydricalcohols which are derived by leaving active hydrogen atoms as protonson the alcoholic hydroxyl groups, for example, ethylene glycol,propylene glycol, diethylene glycol, dipropylene glycol, 1,3-propandiol,1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanediol,trimethylolpropane, glycerin, diglycerin, pentaerythritol, ordipentaerythritol, and organic oxyanions of monocarboxylates which arederived by leaving active hydrogen atoms as protons existing onα-carbons, for example, methyl acetate, ethyl acetate, cyclohexylpropionate, isopropyl butyrate, methyl isobutyrate, t-butyl isobutyrate,hexyl caproate, butyl laurate, methyl stearate, ethyl oleate, methylphenyl acetate, methyl cyclohexanecarboxylate,1,2-bis(2-propylcarbonyloxy)ethane, or1,2,3-tris(2-propylcarbonyloxy)propane, and organic oxyanions ofcarboxylates which are derived by leaving active hydrogen atoms asprotons existing on α-carbons in carbonyl group, for example, dimethylmalonate, dimethyl methylmalonate, diethyl succinate, butyl2,3-dimethylsuccinate, methyl adipate, ethyl suberate, methylbutanetetracarboxylate, 1,2-bis(2-methoxycabonylethoxy)ethane,1,2-bis(2-ethoxycarbonylpropoxy)ethane,1,2-bis(2-ethoxycarbonylpropylmercapto)ethane,N,N,N′,N′-tetrakis(2-butoxycarbonylpropyl)ethylenediamine or oligo orpoly(methyl methacrylate) having average molecular weight of 200 to1,000,000, and organic oxyanions of ketocarboxylates which are derivedby leaving active hydrogen atoms as protons existing on α-carbons incarbonyl groups, for example, ethyl acetoacetate, cyclopentylacetoacetate, methyl carbamoylacetate, ethyl2-cyclohexylcarbonylacetate, or butyl benzoylacetate.

Among these anions, preferable anions are organic oxyanions derived frommonohydryic alcohols, those derived from monocarboxylates, or thosederived from polycarboxylates and more preferable ones are organicoxyanions derived from monohydric alcohols.

The organic oxysalt compounds used in the present invention are formedby the combination of these organic oxyanions and metal cations ororganic cations described above, and the combination of two or more thantwo kinds of the organic oxysalt compounds may be used.

Quantity of the organic oxysalt can be determined optionally dependingon aimed molecular weight of (co)polymer to be produced and can bedetermined by calculating formulas (1) or (2) described later.

The hydroxycarbonyl compounds used in the present invention have atleast both an alcoholic hydroxyl group and a carbonyl group in the samemolecule, and specific examples of these compounds are α-hydroxyketones,for example, 1-hydroxy-1,1-dimethyl-2-propanone,1-hydroxy-1,1-dimethyl-3,3,3-trimethyl-2-propanone,α-hydroxy-α-methylethylcyclohexylketone,α-hydroxy-α-methyl-α′-methylcyclohexylketone,α-hydroxydicyclohexylketone, α-hydroxy-α′-methyldicyclohexylketone,α-hydroxy-α-methylphenylketone, α-hydroxycyclohexylphenylketone,benzoin, α-hydroxy-α, α-diphenylacetophenone, and α-hydroxycarboxylates,for example, ethyl α-hydroxyacetate, methyl lactate, cyclohexyl lactate,ethyl α-hydroxyacetate, butyl α-hydroxy-iso-butyrate, methylα-hydroxy-α-phenylacetate, ethyl α-hydroxy-α, α-diphenylacetate, andα-hydroxy-N,N-disubstituted amides, for example,α-hydroxy-N,N-dimethylacetamide, α-hydroxy-α,α-dimethyl-N,N-dimethylacetamide, α-hydroxy-α,α-diphenyl-N,N-dimethylacetamide, α-hydroxy-N,N-diethylpropionamide orα-hydroxy-α-methyl-N,N-diethylpropionamide. As other examples, anyhydroxyketone compounds may be used as far as they do not hinder thepurposes of the present invention and two or more than two kinds ofhydroxyketone compounds described above may be used together.

Among these compounds, preferable α-hydroxyketones are, for example,1-hydroxy-1,1-dimethyl-2-propanone,1-hydroxy-1,1-dimethyl-3,3,3-trimethyl-2-propanone,α-hydroxy-α-methylethylecyclohexylketone,α-hydroxy-α-methylethyl-α′-methycyclohexylketone,α-hydroxydicyclohexylketone, α-hydroxydicyclohexylketone,α-hydroxy-α-methylphenylketone, α-hydroxycyclohexylphenylketone,benzoin, α-hydroxy-α, α-diphenylacetophenone, and α-hydroxycarboxylates,for example, ethyl α-hydroxyacetate, methyl lactate, cyclohexyl lactate,ethyl α-hydroxybutyrate, butyl α-hydroxyisobutyrate, methylα-hydroxy-α-phenylacetate, ethyl α-hydroxy-α, α-diphenylacetate, andmore preferable α-hydroxyketones are, for example, α-hydroxyacetone,1-hydroxy-1,1-dimethyl-2-propanone,1-hydroxy-1,1-dimethyl-3,3,3-trimethyl-2-propanoneα-hydroxy-α-methylethylcyclohexylketone,α-hydroxy-α-methylethyl-α′-methylcyclohexylketone,α-hydroxydicyclohexylketone, α-hydroxy-α′-methyldicyclohexylketone,α-hydroxy-α-methylethylphenylketone, α-hydroxycyclohexylphenylketone,benzoin, α-hydroxy-α, α-diphenylacetophenone.

Quantity of the hydroxyketone to be used is usually more than 0.05moles, preferably 0.80 to 1.20 moles, more preferably 0.95 to 1.05 moleto one mole of the organic oxysalt compound. Excess quantity of thehydroxyketone acts as a chain transfer agent.

In the present invention it is possible to achieve stoichiometric andcatalytic living polymerization of polar unsaturated compound usingorganic oxysalt compound as catalyst in the presence of hydroxycarbonylcompounds having at least both an alcoholic hydroxyl group and acarbonyl group in the same molecule. More specifically, {circumflex over(1)} the stoichiometric living polymerization can be performed bycontacting organic oxysalt compounds with polar unsaturated compoundsfor polymerization in the presence of hydroxycarbonyl compounds havingat least both an alcoholic hydroxyl group and a carbonyl group in thesame molecule, and {circumflex over (2)}the catalytic livingpolymerization can further be carried out using active hydrogen compoundas chain transfer agent. Since in both cases the polymerization proceedslivingly, the average molecular weight and the number of the moleculesof the (co)polymer to be produced may be calculated and predictedapproximately by the following calculation formulas (1) or (2) whereinMwa indicates the molecular weight of the oxyanion in the organicoxysalt compound; Mb indicates the number of moles of polar unsaturatedcompound; Ma indicates the number of moles of the said oxyanion; MWbindicates the molecular weight of the polar unsaturated compound; MWcindicates the molecular weight of the chain transfer agent; Mc indicatesthe number of moles of the chain transfer agent.

{circumflex over (1)} (co)polymer obtained by stoichiometric livingpolymerization:

<number average molecular weight>≈Mwa+(Mb/Ma)×MWb

<number of molecules of the produced (co)polymer>≈(number of the saidorganic oxysalt compound)  (1)

{circumflex over (2)} (co)polymer obtained by catalytic livingpolymerization:

<number average molecular weight>≈(MWa×Ma+MWc×Mc+Mb×MWb)/(Ma+Mc)

<number of molecules of the produced (co)polymer>≈(number of moleculesof the said organic oxysalt compound+number of the molecule of the chaintransfer agent).  (2)

As can be seen from the calculation formulas described above, accordingto the methods of the present invention it is possible to produce a(co)polymer having optionally controlled number average molecular weightand number of the produced (co)polymer by adjusting molecular weight andnumber of moles of the organic oxysalt compound, polar unsaturatedcompound or chain transfer agent, i.e., active hydrogen compound to beused.

In the method of the present invention, the unsaturated group isunsaturated group having one to four valences derived from alkene andthe polar unsaturated compound is the chemical compound having polarfunctional group and unsaturated group in the same molecule selectedfrom the group consisting of carbonyl, cyano, and pyridyl, and, inaddition, the functional group and the unsaturated group form a director indirect conjugated systems.

These chemical compounds are, for example, (1) (meth)acrylates, (2)(meth)acrylonitriles, (3) (meth)acrylamides, (4) vinylpyridines, (5)N-substituted maleimides, (6) vinylketones, or styrene derivatives. Anypolar unsaturated compounds may be used as far as they can achieveanionic polymerization by the method of the present invention.

As specific examples, (1) (meth)acrylates are esters of acrylic acid ormethacrylic acid. These esters are, for example:

(1){circumflex over (1)} monoesters formed by esterification betweenmonohydric alcohols and acrylic acid or methacrylic acid: these estersare, for example, methyl acrylate, methyl methacrylate, ethyl acrylate,propyl methacrylate, butyl acrylate, 2-ethylhexyl methacrylate, laurylacrylate, stearyl methacrylate, 1,1,1,3,3,3-hexafluoroisopropylacrylate, 1,1,1,3,3,3-hexafluoroisopropyl methacrylate,2,2,2-trifluoroethyl acrylate, 2,2,2-trifluoroethyl methacrylate,1H,1H,2H,2H-heptadecafluorodecyl acrylate, allyl acrylate, allylmethacrylate, cyclohexyl methacrylate, isophenyl acrylate, glycidylacrylate, glycidyl methacrylate, tetrahydrofurfuryl acrylate, benzylacrylate or β-phenylethyl methacrylate.

(1)-{circumflex over (2)} Monoesters formed by esterification betweendihydric alcohols whose one end is protected by an ether bond andacrylic acid or methacrylic acid: these esters are, for example,2-methoxyethyl acrylate, 2-ethoxyethyl methacrylate, 2-phenoxyethylacrylate, 2-dicyclopentenyloxyethyl acrylate, 1-methoxy-2-propylmethacrylate, 3-methoxypropyl acrylate, 4-ethoxybutyl methacrylate,6-methoxyhexamethyl acrylate, methoxydiethylene glycol acrylate,phenoxydipropylene glycol methacrylate, ethoxytripropylene glycolmethacrylate, ethoxypolyethylene glycol acrylate, ormethoxypolypropylene glycol methacrylate.

(1)-{circumflex over (3)} Polyesters formed by esterification betweenacrylic acid or methacrylic acid and all of the hydroxyl groups ofdihydric alcohols and polyhydric alcohols having more than two hydroxylgroups: these esters are, for example, ethylene glycol diacrylate,ethylene glycol dimethacrylate, propylene glycol diacrylate, propyleneglycol dimethacrylate, 1,3-propanediol dimethacrylate, 1,4-butanedioldiacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol diacrylate,neopentyl glycol dixnethacrylate, diethylene glycol diacrylate,dipropylene glycol dimethacrylate, triethylene glycol dimethacrylate,tripropylene glycol diacrylate, polyethylene glycol diacrylate,polypropylene glycol diacrylate, or polypropylene glycol dimethacrylate,and, in addition, glycerin triacrylate, glycerin trimethacrylate,pentaerthritol tetramethacrylate, dipentaerythritol hexaacrylate,trimethylolpropane triacrylate, poly(ethylene oxide)triol triacrylate,poly(propylene oxide)triol triacrylate, or poly(propylene oxide)trioltrimethacrylate.

(1)-{circumflex over (4)} Esters formed by esterification betweenalcohols containing ester bonds and acrylic acid or methacrylic acid:these esters are, for example, 2-benzoyloxyethyl acrylate,2-benzoyloxyethyl methacrylate, 2-acetyloxy acrylate,5-tetrahydrofurfuryloxycarbonylpentyl acrylate,5-tetrahydrofurfuryloxycarbonylpentyl methacrylate,2,2,6,6-tetramethyl-4-oxy-5-oxa-heptane-1,7-diyl-diacrylate.

(1)-{circumflex over (5)} Esters formed by esterification betweenalcohols having cycloacetal bond and acrylic acid or methacrylic acid:these esters are, for example, 2-t-butyl-1,3-dioxycyclopentane-2′-ilmethacrylate, or2-t-butyl-5-ethyl-5-vinylcarbonyloxymethyl-1,3-dioxycyclohexane-2′(2)-ilacrylate.

(1)-{circumflex over (6)} Esters formed by esterification betweenoxysuccinimide and acrylic acid or methacrylic acid: these esters are,for example, N-oxysuccinimide acrylate or N-oxysuccinimide methacrylate.

(1)-{circumflex over (7)} Esters formed by esterification betweenalcohols having secondary amino group and acrylic acid or methacrylicacid: these esters are, for example, 2-dimethylaminoethyl acrylate or2-ethylpropylaminoethyl methacrylate.

(1)-{circumflex over (8)} Esters formed by esterification betweenalcohols having cyano group and acrylic acid or methacrylic acid: theseesters are, for example, 2-cyanoethyl acrylate or 2-cyanopropylmethacrylate.

(2) (Meth)acrylonitriles are, for example, acrylonitrile ormethacrylonitrile.

(3) (Meth)acrylamides are, for example, acrylaniide, N-monosubstitutedor N,N-disubstituted(meth)acrylamides. One of these compounds is, forexample, acrylamide.

(3)-{circumflex over (1)} N-monosubstituted (meth)acrylamides: thesecompounds are, for example, N-methylacrylamide, N-ethylacrylamide,N-propylacrylamide, N-butylacrylamide, N-octylacrylamide,N-phenylacrylamide, N-glycidylacrylamide, or N,N′-ethylenebisacrylamide.

(3)-{circumflex over (2)} N,N-disubstituted mono(meth)acrylamides: thesecompounds are, for example, N,N-dimethylacrylamide,N-ethyl-N-methylacrylamide, N,N-diethylacrylamide,N,N-di-n-propylacrylamide, N,N-dioctylacrylamide,N,N-diphenylacrylamide, N-ethyl-N-glycidylacrylamide,N,N-diglycidylacrylamide, N-methyl-N-(4-glycidyloxybutyl)acrylamide,N-methyl-N-(5-glycidyloxypentyl)acrylamide,N-methyl-N-(6-glycidyloxyhexyl)acrylamide, N-acryloylpyrrolidine,N-acryloyl-L-proline methyl ester, N-acryloylpiperidine,N-acryloylmorpholine or 1-acryloylimidazole.

(3)-{circumflex over (3)} N,N′-disubstituted bis(meth)acrylamides: thesecompounds are, for example, N,N′-diethyl-N,N′-ethylenebisacrylamide,N,N′-dimethyl-N,N′-hexamethylenebisacrylamide or(N,N′-ethylene)bisacrylamide.

(4) Vinylpyridines are, for example, vinyl or isopropenyl substituted

pyridines such as 2-vinylpyridine, 2-isopropenylpyridine, or4-vinylpyrideine.

(5) N-substituted maleimides: these compounds are, for example,

(5)-{circumflex over (1)} N-aliphatic substituted maleimides: thesecompounds are, for example, N-methylmaleimide or N-ethylmaleimide.

(5)-{circumflex over (2)} N-aromatic substituted maleimides: thesecompounds are, for example, N-phenylmaleimide orN-(4-methylphenyl)maleimide.

(6) Vinylketones: These compounds are, for example, methylvinylketone,isopropenylmethylketone, ethylvinylketone, ethylisopropenylketone,butylvinylketone, or phenylvinylketone.

(7) Styrene derivatives: These compounds are, for example,p-methoxycarbonyl styrene, p-t-butoxycarbonylstyrene, or p-cyanostyrene.These polar unsaturated compounds may have any substituents other thanthose described above as far as they do not hinder the methods of thepresent invention.

Among these unsaturated compounds, preferable ones are, for example, asfollows:

(1)-{circumflex over (1)} Monoesters formed by esterification betweenmonohydric alcohols and acrylic acid or methacrylic acid: these estersare, for example, methyl acrylate, methyl methacrylate, ethyl acrylate,propyl methacrylate, butyl acrylate, 2-ethylhexyl methacrylate, laurylacrylate, stearyl methacrylate, 1,1,1,3,3,3-hexafluoroisopropylacrylate, 1,1,1,3,3,3-hexafluoroisopropyl methacrylate,2,2,2-trifluoroethyl acrylate, 2,2,2-trifluoroethyl methacrylate,1H,1H,2H,2H-heptadecafluorodecyl acrylate, allyl acrylate, allylmethacrylate, cyclohexyl methacrylate, isophenyl acrylate, glycidylacrylate, glycidyl methacrylate, tetrahydrofurfuryl acrylate, benzylacrylate or β-phenylethyl methacrylate.

(1)-{circumflex over (2)} Monoesters formed by esterification betweendihydric alcohols whose one end is protected by an ether bond andacrylic acid or methacrylic acid: these esters are, for example,2-methoxyethyl acrylate, 2-ethoxyethyl methacrylate, 2-phenoxyethylacrylate, 2-dicyclopentenyloxyethyl acrylate, 1-methoxy-2-propylmethacrylate, 3-methoxypropyl acrylate, 4-ethoxybutyl methacrylate,6-methoxyhexyl acrylate, methoxydiethylene glycol acrylate,phenoxydipropylene glycol methacrylate, ethoxytripropylene glycolmethacrylate, ethoxypolyethylene glycol acrylate, ormethoxypolypropylene glycol methacrylate.

(1){circumflex over (3)} Polyesters formed by esterification betweenacrylic acid or methacrylic acid and all of the hydroxyl groups of apolyhydric alcohol having two or more than two hydroxyl groups: theseesters are, for example, ethylene glycol diacrylate, ethylene glycoldimethacrylate, propylene glycol diacrylate, propylene glycoldimethacrylate, 1,3-propanediol dimethacrylate, 1,4-butanedioldiacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol diacrylate,neopentyl glycol dimethacrylate, diethylene glycol diacrylate,dipropylene glycol dimethacrylate, triethylene glycol dimethacrylate,tripropylene glycol diacrylate, polyethylene glycol diacrylate,polypropylene glycol diacrylate, polypropylene glycol dimethacrylate,and, in addition, glycerin triacrylate, glycerin trimethacrylate,pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate,trimethylolpropane triacrylate, poly(ethylene oxide)triol triacrylate,poly(propylene oxide)triol triacrylate, or poly(propylene oxide)trioltrimethacrylate.

(2) Acrylonitrile or methacrylonitrile

(3)-{circumflex over (2)} N,N-disubstituted mono(meth)acrylamides: thesecompounds are, for example, N,N-dimethylacrylamide,N-ethyl-N-methylacrylamide, N,N-diethylacrylamide,N,N-di-n-propylacrylamide, N,N-dioctylacrylamide,N,N-diphenylacrylamide, N-ethyl-N-glycidylacrylamide,N,N-diglycidylacrylamide, N-methyl-N-(4-glycidyloxybutyl)acrylamide,N-methyl-N-(5-glycidyloxypentyl)acrylamide,N-methyl-N-(6-glycidyloxyhexyl)acrylamide, N-acryloylpyrrolidine,N-acryloyl-L-proline methyl ester, N-acryloylpiperidine,N-acryloylmorpholine or N-acryloylimidazole.

(4) Vinyl or isopropenyl substituted pyridines: these compounds are, forexample, 2-vinylpyridine, 2-isopropenylpyridine, or 4-vinylpyrideine.

(5)-{circumflex over (2)}N-aromatic maleimides: these compounds are, forexample, N-phenylmaleimide or N-(4-methylphenyl)maleimide; and

(6) vinylketones: these compounds are, for example, methylvinylketone,isopropenylmethylketone, ethylvinylketone, ethylisopropenylketone,butylvinylketone, or phenylvinylketone.

More preferable polar unsaturated compounds as described above are asfollows:

(1)-{circumflex over (1)} Monoesters formed by esterification betweenmonohydric alcohols and acrylic acid or methacrylic acid;

(1)-{circumflex over (2)} monoesters formed by esterification betweendihydric alcohols whose one end is protected by an ether bond andacrylic acid or methacrylic acid;

(1)-{circumflex over (3)} polyesters formed by esterification betweenacrylic acid or methacrylic acid and all of the hydroxyl groups ofpolyhydric alcohols having two or more than two hydroxyl groups;

(2) acrylonitrile or methacrylonitrile; and

(3) N,N-disubstituted mono(meth)acrylamides.

In the present invention, the polar unsaturated compound can be usedalone or in combination with two or more of them.

In case of applying plural compounds together, there may be a method ofsimultaneous application, that of sequential one or that of repeatingsequential ones. When plural monomers are polymerized togethersimultaneously, higher random copolymers are obtained depending on thereactivity of the compounds and when two or more than two monomers arepolymerized in sequential order, block polymers containing two or morethan two blocks are obtained. When repeating the simultaneous andsequential polymerization, further complicated copolymers are obtained.

In the present invention an active hydrogen compound is used as chaintransfer agent when catalytic living polymerization is carried out.

As the active hydrogen compounds there are, for example, active hydrogencompounds having active hydrogen on carbon atom, those having activehydrogen on oxygen atom, those having active hydrogen on nitrogen atom,or those having active hydrogen on sulfur atom. Any other activehydrogen compounds may be used as far as they do not hinder the methodsof the present invention.

Specific examples of the active hydrogen compounds having activehydrogen on carbon atom are, for example, monocarboxylates such as ethylacetate, cyclohexyl propionate, isopropyl butyrate, methyl isobutyrate,t-butyl isobutyrate, hexyl caproate, butyl laurate, methyl stearate,ethyl oleate, methyl phenylacetate, methyl cyclohexanecarboxylate,1,2-bis(2-propylcarbonyloxy)ethane, or1,2,3-tris(2-propylcarbonyloxy)propane; polycarboxylates such asdimethyl malonate, dimethyl methylmalonate, diethyl succinate, butyl2,3-dimethylsuccinate, methyl adipate, ethyl suberate, methylbutanetetracarboxylate, 1,2-bis(2-methoxycarbonylethoxy)ethane,1,2-bis(2-ethoxycarbonylpropoxy)ethane,1,2-bis(2-ethoxycarbonylpropylmercapto)ethane,N,N,N′,N′-tetrakis(2-butoxycarbonylpropyl)ethylenediamine;ketocarboxylates such as ethyl acetoacetate, cyclopentyl acetoacetate,methyl carbamoylacetate, ethyl 2-cyclohexylcarbonylacetate, or butylbenzoylacetate; nitriles such as acetonitrile,2-cyanopropane,malononitrile, methylmalononitrile, 1,3-dicyanopropane, or adiponitrile;ketones such as acetone, methylethylketone, diisopropylketone,dicyclohexylketone, acetophenone, or isopropylphenylketone.

Specific examples of the active hydrogen compounds having activehydrogen on nitrogen atom are monohydric alcohols such as menthol,ethanol, n-propanol, isopropanol, n-butyl alcohol, sec-butyl, alcohol,tert-butyl alcohol, isopentyl alcohol, tert-pentyl alcohol, n-octylalcohol, lauryl alcohol, cetyl alcohol, cyclopentanol, cyclohexanol,allyl alcohol, crotyl alcohol, methylvinylcarbinol, benzyl alcohol,1-phenylethyl alcohol, triphenylcarbinol, cinnamyl alchohol,perfluoro-tert-butyl alcohol, α-hydroxyisopropylphenylketone,α-hydroxycyclohexylphenylketone, or methyl α-hydroxyisobutyrate;polyhydric alcohols such as ethylene glycol, propylene glycol,diethylene glycol, dipropylene glycol, 1,3-propandiol, 1,3-butanediol,1,4-butaneidol, 1,6-hexanediol, 1,4-cyclohexanediol, trimethylolpropane,glycerin, diglycerin, pentaerythritol, or dipentaerythritol; aromatichydroxy compounds such as phenol, cresol, xylenol, 2-naphthol,2,6-dihydroxynaphthalene, or bisphenol A.

Specific examples of the active hydrogen compounds having activehydrogen on nitrogen atom are aliphatic or aromatic primary amines suchas methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine,isobutylamine, sec-butylamine, tert-butylamine, cyclohexylamine,benzylamine, β-phenylethylamine, aniline, o-toluidine, m-toluidine, orp-toluidine; aliphatic or aromatic secondary amines such asdimethylamine, methylethylamine, diethylamine, di-n-propylamine,ethyl-n-butylamine, methyl-sec-butylamine, dipentylamine,dicyclohexylamine, N-methylaniline, or diphenylamine; polyamines havingprimary or secondary amino groups such as ethylenediamine,di(2-aminoethyl)amine, hexamethylenediamine,4,4′-diaminodiphenylmethane, tri(2-aminoethyl)amine, N,N′-dimethylethylenediamine, N,N′-diethylethylenediamine, or(2-methylaminoethyl)amine; saturated cyclic secondary amines such aspyrrolidine, piperidine, morpholine, or 1,2,3,4-tetrahydroquinoline;unsaturated cyclic secondary amines such as 3-pyrroline, pyrrole,indole, carbazole, imidazole, pyrazole, or purine; cyclic polyaminescontaining secondary amino groups such as piperazine, pyrazine, or1,4,7-triazacyclononane; unsubstituted or N-monosubstituted acid amidessuch as acetamide, propionamide, N-methylpropionamide, N-methylbenzoicacid amide, or N-ethylstearic acid amide; cyclic amides such asβ-propiolactam, 2-pyrrolidone, δ-valerolactam, or ε-caprolactam;dicarboxylic acid imides such as succinimide, maleimide, or phthalimide.

The active hydrogen compounds having active hydrogen on sulfur atom are,for example, monothiols such as methanethiol, ethanethiol,n-butanethiol, t-butanethiol, hexanethiol, decanethiol,cyclopentylmercaptan, or cyclohexylmercaptan; polythiols such as1,2-ethanedithiol, 1,3-propanedithiol, 2,3-butanedithiol,1,6-hexanedithiol, 1,2,3-propanetrithiol, or2,3-di(mercaptomethyl)-1,4-butanedithiol; aromatic mercapto compoundssuch as thiophenol, o-thiocresol, thionaphthol, or 1,2-benzenedithiol.

As further active hydrogen compounds there are poly(alkyleneoxides)having active hydrogen at the end of the molecule such aspolyethyleneoxide or polypropyleneoxide;(co)poly{(meth)acrylates},(co)poly{(meth)acrylonitriles},(co)poly(acrylamides), (co)poly(vinylpyridines), (co)Poly(N-substitutedmaleimides), (co)poly(vinylketones), or (co)poly(styrene derivatives)which have active hydrogen at the ends of the molecule and/or in thebackbone chain, and furthermore, (co)polyesters, (co)polyamides,(co)polylactides, and (co)polysiloxane.

The active hydrogen compounds as described above act as chain transferagent. Although the mechanism of the action is not necessarily clearlyunderstood, it might be interpreted as follows: Since the equilibriumreaction proceeds reversibly and quite rapidly between new anionsgenerated by the addition of organic oxyanions composing organic oxysaltcompounds to polar unsaturated compounds and parts having activehydrogen atoms, the active hydrogen atoms are separated as protons fromthe parts having the active hydrogen atoms and are attracted toward theanions resulting in starting of polymerization also from the parts. Thesaid active hydrogen compounds include chemical compounds having pluralnumber of active hydrogen and whether the polymerization starts from allthe parts having active hydrogen or from a part of them depends upon thedegree of dissociation of the said active hydrogen, the reactivity ofthe attracted anion, the kind of the polar unsaturated compound, or thekind of the solvent applied.

The active hydrogen compound can be used alone or in combination of twoor more of them simultaneously.

Among these active hydrogen compounds, preferable ones aremonocarboxylates such as ethyl acetate, cyclohexyl propionate, isopropylbutyrate, methyl isobutyrate, t-butyl isobutyrate, hexyl caproate, butyllaurate, methyl stearate, ethyl oleate, methyl phenyl acetate, methylcyclohexanecarboxylate, 1,2-bis(2-propylcarbonyloxy)ethane or1,2,3-tris(2-propylcarbonyloxy)propane; polycarboxylates such asdimethyl malonate, dimethyl methylmalonate, diethyl succinate, butyl2,3-dimethylsuccinate, methyl adipate, ethyl suberate, methylbutanetetracarboxylate, 1,2-bis(2-methoxycabonylethoxy)ethane,1,2-bis(2-ethoxycarbonylpropoxy)ethane,1,2-bis(2-ethoxycarbonylpropylmercapto)ethane,N,N,N′,N′-tetrakis(2-butoxycarbonylpropyl)ethylenediamine; monoalcoholssuch as methanol, ethanol, n-propanol, isopropanol, n-butyl alcohol,sec-butyl alcohol, tert-butyl alcohol, isopentyl alcohol, tert-pentylalcohol, n-octyl alcohol, lauryl alcohol, cetyl alcohol, cyclopentanol,cyclohexanol, allyl alcohol, crotyl alcohol, methylvinylcarbinol, benzylalcohol, 1-phenylethyl alcohol, triphenylcarbinol, or cinnamyl alcohol,perfluoro-tert-butyl alcohol, α-hydroxyisopropylphenylketone,α-hydroxycyclohexylphenylketone, or methyl α-hydroxyisobutyrate;polyhydric alcohols such as, ethylene glycol, propylene glycol,diethylene glycol, dipropylene glycol, 1,3-propandiol, 1,3-butanediol,1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanediol, trimethylolpropane,glycerin, diglycerin, pentaerythritol, or dipentaerythritol; monothiolssuch as methanethiol, ethanethiol, n-butanethiol, t-butanethiol,hexanethiol, decanethiol, cyclopentylmercaptan, or cyclohexylmercaptan;(co)poly(alkyleneoxide) having active hydrogen at the end and/or in thebackbone chain, (co)poly{(meth)acrylates},(co)poly{(meth)acrylonitriles}, (co)poly(acrylamides),(co)poly(vinylpyridines), (co)poly(N-substituted maleimides),(co)poly(vinylketones), or (co)poly(styrene derivatives).

The modes of the polymerization of the present invention are notparticularly limited. Usually, after contacting hydroxyketone compoundor a solution of the compound prepared by dissolving in suitablesolvent, if necessary, with organic oxysalt compound, chain transferagent to be used is added, and then polar unsaturated compound iscontacted to polymerize it. If necessary, in a batch method of chargingthem together, the said unsaturated compound may also be chargedintermittently or continuously. In case of obtaining copolymers, inaccordance with the desired forms of copolymers the methods of chargingplural number of these polar unsaturated compounds all together,intermittently, or continuously or the method of charging the pluralnumber of polar unsaturated compounds in sequential order may beadopted. Quantity of the organic oxysalt compound to be used is notparticularly restricted and usually 1×10⁻⁷ to 1×10⁻¹ moles to 1 mole ofthe said polar unsaturated compound and preferably in the range of1×10⁻⁴ to 3×10⁻¹ moles. Quantity of the hydroxyketone compound to beused is usually 0.05 moles and more, preferably 0.5 to 1.50 moles, andmore preferably 0.95 to 1.05 moles to 1 mole of the organic oxysaltcompound. Quantity of the chain transfer agent, i.e., the activehydrogen compound varies. It depends on the molecular weight of the(co)polymer to be produced and usually 1×10⁻⁶ to 5×10⁻¹ moles to 1 moleof the polar unsaturated compound and preferably in the range of 1×10⁻⁴to 2×10⁻¹ moles. The temperature of the polymerization varies. Itdepends upon the organic oxysalt compound, hydroxyketone compound, thechain transfer agent to be used, and the kinds and quantity of the saidpolar unsaturated compound. It is usually −50° C. to 250° C., preferablyin the range of −20° C. to 150° C. The pressure of the polymerizationvaries. It depends on the kinds, quantity, and the reaction temperature,and is usually below 3.0 MPa (absolute pressure in mega pascal, the samein the following), preferably 0.01 to 1.5 MPa, more preferably 0.1 to1.0 MPa.

The reaction time required for the polymerization depends on the organicoxysalt compound and the hydroxyketone compound which are used, thekinds and quantity of the chain transfer agent to be used and the saidpolar unsaturated compound. The reaction temperature is usually within50 hours and preferably 0.1 to 24 hours.

Usually the said polar unsaturated compound contains a trace of apolymerization inhibitor, however in the method of the present inventionthe polymerization may be carried out in the presence of thepolymerization inhibitor.

The polymerization in the method of the present invention may be carriedout in a molten state of the said polar unsaturated compound. Ifnecessary, suitable solvent may also be used. The polymerization mayproceed in homogeneous solution or in suspension. The solvent is, forexample, aliphatic or alicyclic hydrocarbon such as n-hexane, n-heptane,or cyclohexane; aromatic hydrocarbon such as benzene, toluene, orxylene; aromatic halogenated aromatic compound such as chlorobenzene ordichlorobenzene; ether such as diethyl ether, diphenylether,tetrahydrofuran, tetrahydropyran, 1,4-dioxane, ethylene glycol dimethylether, or diethylene glycol diethyl ether; aprotic polar solvent such asdimethylformamide, dimethyl sulfoxide, sulfolane, orN,N′-dimethylimidazolidinone. Any other solvents may be adopted as faras they do not hinder the methods of the present invention.

The cation, which formed organic oxysalt compound, remains at all or apart of a growth end of the product (co)polymer as counter ion when thepolymerization is ended. For the purpose of separating out the(co)polymer stably, the polymerization may be terminated by addinginorganic acid such as hydrochloric acid, sulfuric acid, or phosphoricacid or organic acid such as acetic acid, propionic acid,benzenesulfonic acid, or paratoluenesulfonic acid and convert the saidcation to the salt of inorganic or organic acid. The produced(co)polymer may be used, for the next purposes, as it is, or may be usedfor the next purposes, after the termination of the polymerization, byonly solidifying the product by distilling out the solvent used, whennecessary; however usually it is possible to separate out the(co)polymer by precipitating method of adding the reaction liquid itselfor the solution wherein the dry solid is dissolved in suitable solventto poor solvent. It is also possible to purify the (co)polymer byrepeating the precipitating method.

The third invention obtained by the method of the present invention,that is, thermosetting powder coating composition made of the(co)polymer(A) obtained by the method of the present invention will beexplained.

As (co)polymer(A), (co)polymer of one or more kinds of polar unsaturatedcompound containing epoxy group obtained by the method as described inany one of [1] to [12] or (co)polymer of the said polar unsaturatedcompound containing epoxy group and polar unsaturated compound is used.

As polar unsaturated compound containing epoxy group, any unsaturatedcompound may be used without particular limitation as far as it containsepoxy group and typical examples of the compound are polar unsaturatedcompound containing epoxy group such as glycidyl methacrylate, glycidylacrylate, β-methylglycidyl methacrylate, β-methylglycidyl acrylate,acrylglycidyl ether and one kind or combination of two or more than twokinds of these compounds may be used.

As polar unsaturated compound which may be copolymerized with polarunsaturated compound containing epoxy group there is no particularlimitation as far as polar unsaturated compound is concerned, and thetypical examples of the compound are monomers of acrylates ormethacrylates having alkyl or cyclohexyl group having 1 to 14 carbons,for example, acrylic acid derivatives or methacrylic acid derivativesincluding methyl-, ethyl-, n-propyl-, isopropyl-, n-butyl-, isobutyl-,n-amyl-, isoamyl-, n-hexyl-, cyclohexyl-, 2-ethylhexyl-, octyl-,2-ethyloctyl-, decyl-, dodecyl-, and cyclohexyl-acrylates ormethacrylates, and one kind or mixture and combination of two or morethan two kinds of these compounds may be used.

As other specific examples of the polar unsaturated compound, there areother ethylenic unsaturated monomers, for example, aromatic vinylcompounds such as styrene, α-methylstyrene and vinyltoluene;dicarboxylates such as maleic acid and itaconic acid; unsaturatedmonomers of ethylene halides such as vinyl chloride, vinylidenechloride, vinyl fluoride, monochlorotrifluoroetylene,tetrafluoroethylene, chloroprene; nitriles such as acrylonitrile andmethacrylonitrile; vinyl esters such as vinyl acetate and vinylpropionate; α-olefins such as ethylene, propylene, isoprene, butadiene,α-olefins having 4 to 20 carbon atoms; alkylvinyl ethers such aslaurylvinyl ether; vinyl compounds containing nitrogen such asvinylpyrrolidone and 4-vinylpyrrolidone; one kind or mixture andcombination of two or more than two kinds of these monomers may be used.

In the method of the present invention, content of the polar unsaturatedcompound containing epoxy group in the (co)polymer(A) is 15 to 100 mole%, preferably 20 to 60 mole % of the total monomers.

In the light of storage stability of the powder coating composition andsurface flatness of the paint film caused by reduction in fluidity ofthe coating composition during the baking of the coatings, the glasstransition temperature of the (co)polymer(A) is preferably 10 to 100°C., more preferably, 20 to 70° C. Better storage stability is obtainedwhen the glass transition temperature is above 10° C. and preferablemelt viscosity is obtained resulting in better external appearance ofpaint film when it is below 100° C.

In the present invention the glass transition temperature is measuredusing robot DSC RDC220 (Seikou Denshi Kougyou's product) at 10° C./min.from −20 to 120° C. The definition of the glass transition temperatureis described in page 131 of Koubunshi Jiten (Koubunshi Gakkai Henshuu,Asakura Shoten Hakkou, Shouwa 46 Nen Shohan)

As the curing agent composition component (B), which can cure the(co)polymer(A) as described above, to be used for the thermosettingpowder coating composition of the present invention, the compounds whichcan cure the (co)polymer(A) by reacting with the functional groups inthe (co)polymer(A) are used. However when the said functional group isepoxy, at least one kind of compound selected from the group consistingof polycarboxylic acid and/or polycarboxylic acid anhydride ispreferable. The compound is the component of the composition of curingagent which reacts with the epoxy groups existing in the molecule of thecomposition of resin to be used for the powder coatings of the presentinvention.

As the compound of polycarboxylic acid any aliphatic, aromatic, andalicyclic compound may be used. Specific examples of the aromaticpolycarboxylic acids are isophthalic acid and trimellitic acid and theseacids may be used as single or the combination of them. Specificexamples of the alicyclic polycarboxylic acids are hexahydrophthalicacid and tetrahydrophthalic acid and these acids may be used as singleor the combination of them. Polyester resin having carboxyl group may beused also. However, in the present invention the compound of aliphaticpolycarboxylic acid is preferably used in the light of the paint filmproperty such as the surface flatness and the weather resistance.

There is no particular limitation regarding the aliphatic polycarboxylicacid (b-1) as far as it is aliphatic compound having substantially atleast 2 carboxylic groups in the molecule and one or more than one kindsof the aliphatic compound may be used.

Specific examples of the aliphatic polycarboxylic acid (b-1) arealiphatic dicarboxylic acid. As specific examples of the aliphaticdicarboxylic acid are those having carbon number of around 4 to 24 suchas succinic acid, glutaric acid, adipic acid, pimelic acid, subericacid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioicacid, brassidic acid, octadecanedioic acid, and eicosanedioic acid, andthe dodecanedioic acid is preferable among them and these acids are usedsingly or in combination of them.

The polycarboxylic acid anhydride (b-2) in the present invention is notparticularly limited as far as the acid anhydride is a compound whichcontain aliphatic acid anhydrides of linear oligomer of more thandimmers or polymers substantially having or not having carboxyl groupsin the molecule and have at least 2 carboxyl groups and/or acidanhydride groups existing substantially in the molecules, and one ormore than one kinds of the polycarboxylic acid anhydrides may be used.An example of the polycarboxylic acid anhydride is a dehydrationcondensation product of the polycarboxylic acid (b-1). Among them linearcondensed anhydride of dodecandioic acid is preferable and its typicalexample is Additol XVL1381 (Sorushia's product). The polycarboxylic acidanhydride (b-2) is preferably prepared so that the melting point is inthe range of 40 to 150° C.

In the method of the present invention various additives can be addedwhich are usually added to coatings. The external appearance or thepaint film property may also be improved by adequate blending syntheticresin composition containing epoxy resin, polyester resin, or polyamide,natural resin or semi-synthetic resin composition containing celluloseor cellulose derivatives with the thermosetting powder coatingcomposition of the present invention depending on the purpose of use.

Additives such as curing catalyst, pigment, fluidity adjusting agent,thixotropy agent (thixotropy adjusting agent), antistatic agent, surfaceadjusting agent, luster agent, blocking preventing agent, plasticizer,ultraviolet absorbing agent, blowing preventing agent, and slip agentmay be adequately blended with the thermosetting powder coatingcomposition of the present invention depending on the purpose of use. Inthe case of using as clear coat, coloring may be operated by blending asmall amount of pigment so that complete hiding property does not occur.

When composition containing (co)polymer(A) and component (B) are kneadedmechanically, the mixing temperature is not limited particularly as faras substantially homogeneous composition of the powder coating can beprepared. Heating roller, heating kneader, or extruder is usually usedas apparatus for kneading by melting.

As a specific example of the methods for blending the composition of thethermosetting powder coating composition of the present invention, amethod of adequate combination of kneader and blender such as roller,kneading machine, mixer (Banbury type and Transfer type), calendar, orextruder for sufficiently homogeneous mixing at each process conditionadequately chosen (temperature, melting or nonmelting, r.p.m., vacuumatmosphere, and inert atmosphere) may be adopted, and then, a method ofobtaining homogeneous fine powders of the compositions of powdercoatings by pulverizers may be adopted, however these methods are notparticularly limited and there may be other methods than those asdescribed above.

Block of the coating composition obtained by the blending is cooleddown, and then is pulverized so that the mean particle diameter becomes10 to 90 μm. As pulverizers hammer mills are used.

The thermosetting powder coating composition obtained by thepulverization is adhered to the surface of the objects to be coated by amethod of electrostatic coating or fluidized bed one and paint film isformed by thermosetting the composition by heating. In case of theprocess of baking the thermosetting powder coating composition of thepresent invention, it is possible to carry out crosslinking reactionbetween the (co)polymer(A) and the curing agent composition component(B) usually at a temperature of about 100° C. to 180° C., morepreferably, about 120° C. to 160° C., normally for about 10 min. to 60min. After the baking process, paint film having excellent property isobtained by cooling to the room temperature.

When the thermosetting powder coating composition of the presentinvention is used as top coating and not only conventional type coatingsbut also water borne coatings are used as under coating, the paint filmof the coating composition of the present invention after the bakingprocess has as excellent property as in case of using solvent typecoatings.

That is, after under coatings (including those containing pigmentsand/or metal powders) are painted and dried for certain hours, inaccordance with the method as described above the thermosetting powdercoating composition of the present invention is adhered to the surfaceof the under coatings and the paint film is formed by thermosetting thecomposition by heating.

The painting method of the thermosetting powder coating compositionrelated to the present invention are applied to automobile bodies orparts of the automobiles (aluminum wheel, windshield wiper, or centerpillar).

The paint film formed by an appropriate or public known or public usepainting method has excellent property with regard to storage stability(blocking resistance), external appearance (surface flatness,brightness, and transparency), physical property (hardness, scratchresistance, and adhesion property of top coating), and chemical property(weather resistance, acid resistance, and solvent resistance).

EXAMPLE

The present invention is explained by the following examples in moredetail, however these examples are not limiting and should beinterpreted only as for explanation.

Example 1

After a 300 ml flask equipped with a stirrer, a dropping funnel, and atube for temperature measurement was dried sufficiently,2-hydroxy-2,4,4-trimethyl-3-pentanone (169 mg,1.17 mmol) was weighedaccurately and transferred into the flask, and a tetrahydrofuran(abbreviated as THF hereinafter) solution (11.7 ml, 1.17 mmol)containing tetraphenylphosphoniummethoxide (0.10 M) was added to it andstirred to obtain a homogeneous solution. N-butanol (87 mg, 1.17 mmol)as a chain transfer agent was added to the solution and further a THFsolution (176 ml, containing MMA 35.1 g 351 mmol)of methyl methacrylate(abbreviated as MMA)(2.00 M) was dropped so that the reactiontemperature did not exceed 50° C. It took about 30 min. to drop thesolution. After the dropping was completed, the solution was stirred for3 hours and then a THF solution (2.00 ml, 2.00 mmol) of acetic acid (1.0M) was added and the reaction was stopped. A small amount of thereaction mixture was taken and quantitative analysis was carried out bygas chromatography using 1,3,5-trichlorobenzene as an internal standard.As a result of the analysis, the methyl methacrylate and the n-butanolwere completely consumed. The remaining reaction mixture except for 0.5ml to be used for GPC analysis was poured into methanol (about 2 L).Precipitated solid was separated by filtration and washed 3 times withmethanol (40 ml). The obtained solid was dried for 6 hours at 50° C.under 10 mmHg and odorless solid (34.2 g) was obtained. ¹H-NMR and¹³C-NMR spectrum of the solid was almost identical with the poly(methylmethacrylate)of Aldrich Company's product. A solution was prepared sothat the concentration of the poly(methyl methacrylate) became about 0.5wt % by diluting the remaining reaction mixture (0.5 ml) with THF andGPC analysis with standard polymer of poly(methyl methacrylate) wascarried out by means of GPC column(Product of Showa Denkou Co.,connected with 2 columns shodex-KF-803L and shodex-KF-804L)and using THFas developing solvent. As a result of the analysis, the number averagemolecular weight of the obtained poly(methyl methacrylate) was 14,800,while the theoretical number average molecular weight was 15,100 whichwas calculated from the calculating formula(2) of the present inventionand these two figures are quite similar. Furthermore, the molecularweight distribution index (M_(w)/M_(n)) was 1.11, i.e., the distributionis quite narrow, therefore the polymer was found to be monodispersive.The result obtained means that two polymer molecules having similarnumber average molecular weight were produced per one molecule ofcatalyst component.

Examples 2-6

For the purpose of further confirming the property of catalytic livingpolymerization of MMA, the same polymerizations as in Example 1 werecarried out except for changing the amounts of the chain transfer agentn-butanol. In every case, n-butanol and MMA were completely consumed.The results of GPC analysis of the obtained poly(methyl methacrylates)are shown in Table 1 with that of Example 1. The number averagemolecular weights of polymers obtained in each Example are quiteagreeable with those of the theoretical number average molecularweights. The deviation from the theoretical number average molecularweights was within 3% of the theoretical ones. Furthermore, themolecular weight distribution indexes of the polymers obtained were1.06-1.18 which means the polymers were monodispersive ones. The seriesof these results indicate strongly that polymerization of MMA usingorganic oxysalt compounds as catalysts in the presence ofhydroxycarbonyl compounds having at least both alcoholic hydroxyl groupsand carbonyl groups in the same molecules proceeds by the catalyticliving polymerization.

Comparative Example 1

The same polymerization as in Example 1 was carried out except for notusing 2-hydroxy-2,4,4-trimethyl-3-pentanone. The consumption rates ofn-butanol and MMA were 78% and 100%, respectively. The obtained polymerwas the mixture of the polymers having number average molecular weightsof 41,600 and 8,000 and the molecular weight distribution index was4.61. This result and the result obtained in the Example 1 indicate thathydroxyketone compound plays a very important role in the control of thepolymerization.

TABLE 1 Amount of Results of GPC n-butanol used Theoretical AnalysisExample mmol Mn Mn Mw/Mn 1 1.17 15,100 14,800 1.11 2 2.34 10,100 9,9001.18 3 4.68 6,070 6,010 1.16 4 10.5 3,080 2,990 1.09 5 22.2 1,570 1,6001.09 6 23.9 1,100 1,070 1.06 Note: Mn indicates number average molecularweight, Mw/Mn indicates molecular weight distribution.

Application Example

“Part” and “%” in the following explanation are the values based onmass, if not described otherwise.

[Preparation of Painting Plates]

White coating material of acrylic-melamine crosslinking was painted withthickness of 20 μm on a bonderite steel plate having thickness of 0.8 mmwhich has already been treated with zinc phosphate. The steel plate wasthen baked at 140° C. for 30 min and substrate coated steel plate wasprepared.

[Performance Evaluation]

The performance evaluation was made according to the following methods:

{circumflex over (1)} Blocking Resistance Test of Powder CoatingComposition

After storing powder coating composition (6.0 g) for 7 days at 23° C. ina cylindrical container having 20 mm inner diameter, the powder coatingcomposition was taken out and the degree of blocking of the powdercoating composition was evaluated according to ⊚, ◯, and X byeye-observation and contact with fingers.

⊚: quite normal

◯: poor a little bit

X: poor

{circumflex over (2)} External Appearance by Eye-Observation (SurfaceFlatness, Brightness)

External appearances of paint film was evaluated by eye-observationaccording to ⊚, ◯, and X.

⊚: particularly excellent

◯: good

X: poor

{circumflex over (3)} Long Wave(Lw)

Lw was measured by Wave-scan-plus (BYK company's product). The Lw is anindex indicating the surface flatness of paint film.The less the indexvalue is, the more smooth the surface is.

{circumflex over (4)} Luster

Measured values by a glossmeter (60° gloss) were indicated.

{circumflex over (5)} Transparency

Color difference(ΔE) between the paint films to be measured and those ofsubstrate coating was measured by a Color guide (BYK company's product).

⊚: −0.5<ΔE<0.5

X : ΔE≦−0.5 or 0.5≦ΔE

{circumflex over (6)} Hardness Test of the Paint Films

The pencil hardness test (based on Japanese Industrial Standards: JISK5400 6.14) was applied to evaluate the hardness. The indication wasexpressed by pencil hardness symbols.

{circumflex over (7)} Scratch Resistance

Scratching test of rubbing the surface of the paint film by a brushusing a 3% solution of abrasive compound suspension was carried out andluster retention rate was calculated by the evaluation of luster (20°gloss) before and after the rubbing.

Luster retention rate=(20° gloss after the test)/(200 gloss before thetest)×100

The luster retention rate was evaluated according to ⊚, ◯, and X.

⊚: 60% and more

◯: 40% and more, less than 60%

X: less than 40%

{circumflex over (8)} Recoating Property

The test of the recoating property was carried out by the cross-cutadhesion test based on JIS K5400 8.5.2. The number of unpeeled parts wasevaluated according to ⊚, ◯, and X.

⊚: 100

◯: 80 and more, less than 99

X: less than 80

{circumflex over (9)} Acid Resistance

A 10 vol. % solution of sulfuric acid was dropped on the surface of thepaint film and it was left alone at room temperature for one day. Then,the sulfuric acid solution was wiped off and the surface was evaluatedaccording to ⊚, ◯, and X by observation of external appearance.

⊚: No scars were found.

◯: Very few scars were observed.

X: Scars were observed.

{circumflex over (1)}{circumflex over (0)} Solvent Resistance

After rubbing the surface of paint film with a gauze impregnated withxylol for 50 times of reciprocation, the surface was evaluated byobservation according to ⊚, ◯, and X.

⊚: No scars were found.

◯: Very few scars were observed.

X: Scars were observed.

{circumflex over (1)}{circumflex over (1)} Weatherability Test

Acceleration test was carried out according to QSWOM for 2000 hours andluster of the paint film before and after the test was measured and theretention rate of luster(%) was calculated by the following formula:

Retention rate of luster=(20° gloss after the acceleration test)/(20°gloss before the acceleration test)×100

[Polymer (A) Production Example 1]

The (co)polymer (A) of the present invention was evaluated as coatingresin.

Example 7 (Production Example 1)

After a 10 L flask equipped with a stirrer, a dropping funnel ,and atube for temperature measurement was dried sufficiently, hydroxyketonecompound, i.e., 1-hydroxycyclohexylphenylketone (5.37 g, 26.3 mmol) andoxysalt compound, i.e., potassium salt of diethyl methylmalonate (5.33g, 25.1 mmol) were weighed accurately under nitrogen atmosphere at roomtemperature and transferred into the flask. THF (1400 ml) was added tothem and stirred to obtain a homogeneous solution. Methyl isobutyrate(12.8 g, 126 nimol) as chain transfer agent was added to the solution.Then, the solution was cooled with ice. To the solution was dropped a1256 ml THF solution wherein MMA (1.00 M), n-butyl methacrylate(hereinafter abbreviated as n-BMA,0.1 M), isobutyl methacrylate(hereinafter abbreviated as i-BMA, 0.1 M) and glycidyl methacrylate(hereinafter abbreviated as GMA, 0.8 M) are contained respectively(containing 126 g:1.26 mol MMA, 17:9 g:126 mmol n-BMA, 17.9 g:126 mmoli-BMA, 143 g:1.00 mmol GMA) so that the reaction temperature did notexceed 10° C. The time required for the dropping was about 2 hours.After the dropping was completed, the solution was stirred for further 5hours at room temperature and then, the reaction was stopped by addingTHF solution (46.5 ml, 46.5 mmol) of 1.0 M acetic acid. All of themonomers had been consumed completely. Aluminum silicate (25.6 g) wasadded to the reaction mixture and the mixture was stirred for 2 hours atroom temperature and filtered. The mother liquor was concentrated tosolidify it and the obtained solid was dried at 50° C. under 10 mmHg for24 hours. 297 g of colorless and odorless solid was obtained. The glasstransition temperature of the solid was 35° C. and the number averagemolecular weight of the obtained copolymer was 2,410 while itstheoretical number average molecular weight was 2,138 and its molecularweight distribution index was 1.34

[Related Comparative Production Example of (co)polymer(A)]

A flask having 4 inlets equipped with a stirrer, a thermometer, a refluxcondenser, and an inlet for introducing nitrogen was charged with 66.7parts of xylene and heated to the temperature of refluxing. Polarunsaturated compound (parts) and t-butylperoxy 2-ethylhexanoate (PB-O:Nihon Yushi's product) as polymerization initiator as indicated in Table2 were dissolve in the xylene and the mixed solution was dropped during5 hours and was kept at 100° C. for 5 hours thereafter. Polymers(Comparative Production Examples 1, 2, and 3) were obtained by removingthe solvent of the polymer solution which had been produced. Thecharacteristics of the copolymers obtained are also indicated in theTable 2.

TABLE 2 Production Example 1 and Comparative Production Examples 1, 2and 3 Comparative Comparative Comparative Production ProductionProduction Production Example 1 Example 1 Example 2 Example 3 Methyl 5050 35 35 methacrylate n-butyl 5 5 5 5 methacrylate Isobutyl 5 5 5 5methacrylate Glycidyl 40 40 40 40 methacrylate Styrene — — 15 15 PB-O *1— 10 8 13 Number 2410 2480 2300 1720 average molecular weight (Mn)Weight 3220 5780 5150 3510 average molecular weight (Mw) Molecular 1.342.33 2.24 2.04 weight distribution (Mw/Mn) Glass 35 35 35 20 transitiontemperature (° C.) *1: t-butylperoxy 2-ethylhexanoate (Nihon Yushi'sproduct)

Application Examples 1 and 2

Weight ratios (parts) indicated in Table 2 of polymer(A)(ProductionExample 1) and curing agent composition component(B) were blended and1.5 parts of CGL1545 Ciba Geigy Company's product, ultraviolet absorbingagent), 1.5 parts of Chinubin 144 Ciba Geigy Company's product, lightstabilizer), 0.2 parts of benzoin (blowing preventing agent), 0.5 partsof ethylenebisstearamide (blowing preventing agent and slip agent), and1.0 part of Resimix RL-4 (fluidity adjusting agent) were added to thetotal 100 weight parts of (A) and (B), and after the mixture asdescribed above was kneaded in molten state in a kneading machine andcooled, it was pulverized by a pulverizer and powder coating wasobtained. After the produced powder coating was painted on the substratecoated steel plate by the electrostatic spray so that the paint filmthickness became 40 μm, test plate for adhesion test of the top coatingwas obtained by heating the steel plate at 150° C. for 30 min.

[Application Comparative Example 1, 2, 3, and 4]

Except that Application Comparative Polymer ((A) Application ComparativeProduction Examples 1, 2, and 3) and (B) were blended in the ratio asindicated in Table 3, test plate was obtained according to the samemethod as in the Application Example 1.

Evaluation results of Application Examples and Comparative Examples

Evaluation results of the powder coatings and the paint films formed inApplication Examples 1 and 2 are shown in Tables 3 and 4. Evaluationresults of the powder coatings and the paint films formed in ApplicationComparative Examples 1, 2, 3, and 4 relating to the Application Examples1 and 2 are also shown in Tables 3 and 4. The powder coatingscompositions of the Examples as indicated in Table 4 are within thescope of the present invention and the results shown in the tableindicate that the compositions of the present invention are thethermosetting powder coatings compositions which can provides the paintfilms having external appearance (surface flatness, brightness, andtransparency), physical property (hardness, scratch resistance, andrecoating property), and chemical property (weather resistance, acidresistance, and solvent resistance) without lowering the storagestability (blocking resistance) as compared to the conventional powdercoatings.

TABLE 3 Coating compositions of Application Examples 1,2 and ApplicationComparative Examples 1,2,3, and 4 Application Application ApplicationApplication Application Application Comparative Comparative ComparativeComparative Example Example Example Example Example Example 1 2 1 2 3 4Polymer(A) Production 76.8 68.8 Example 1 Comparative Comparative 76.8Polymer Porduction Example 1 Comparative 76.8 68.8 68.8 ProductionExample 2 Hardening Dodecanedioic 23.2 23.2 23.2 agent (B) acidVXL1381*2 31.2 31.2 31.2 *2: Polycarboxylic acid anhydride hardeningagent Additol XVL1381 (Sorushia Company's product)

TABLE 4 Evaluation Results of Application Examples and ApplicationComparative Examples Application Application Application ApplicationApplication Application Comparative Comparative Comparative ComparativeExample Example Example Example Example Example 1 2 1 2 3 4 Blocking ⊚ ⊚◯ ◯ ◯ X resistance Visual ⊚ ⊚ X X X ◯ external appearance Long wave 3.41.9 10.1 12.1 8.9 5.4 Luster 91 91 91 92 92 92 (60° gloss) Transparency⊚ ⊚ ⊚ ⊚ ⊚ ⊚ Paint film H H H H H B hardness Scratch ⊚ ⊚ ⊚ ⊚ ⊚ Xresistance Recoating ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ property Acid ⊚ ⊚ ⊚ ⊚ ⊚ ◯ resistanceSolvent ⊚ ⊚ ⊚ ⊚ ⊚ X resistance Weather 95 95 95 93 93 66 resistance

INDUSTRIAL APPLICABILITY

According to the methods of the present invention, by usinghydroxycarbonyl compounds with inexpensive organic oxysalt compoundwhich has not any particular problem at handling, it is possible toimprove to a great extent the polymerization performance of the saidorganic oxysalt compound to polar unsaturated compound. Furthermore, bypolymerization of polar unsaturated compounds using organic oxysaltcompound as catalyst in the presence of hydroxycarbonyl compound havingat least both an alcoholic hydroxyl group and a carbonyl group in thesame molecule, it is possible to produce quite effectively polymerswhose number average molecular weight and number of produced moleculesare controlled very accurately.

The present invention relates to the thermosetting powder coatingcomposition (for example, acrylic thermosetting powder coatingcomposition) having storage stability, external appearance property,physical property, and chemical property, which have not been achievedyet by the prior arts, and particularly provide thermosetting powdercoating composition (for example acrylic thermosetting powder coatingcomposition) which is particularly applied preferably to the painting,more particularly, to the painting of top coating of automobile bodiesand parts for vehicles such as automobiles (aluminum wheel, windshieldwiper, pillar, door handle, fender, bonnet, air spoiler, stabilizer, andfront grill).

What is claimed is:
 1. A method of producing a living polymerized(co)polymer which method comprises polymerization of polar unsaturatedcompound in the presence of a hydroxycarbonyl compound having at leastboth an alcoholic hydroxyl group and a carbonyl group in the samemolecule using an organic oxysalt compound as catalyst.
 2. The method asclaimed in claim 1, wherein a cation forming the organic oxysaltcompound is an alkali metal cation, a tetraalkylammonium cation, atrialkylsulfonium cation, a tetraarylphosphonium cation, ahexaarylphosphoranilidene ammonium cation, or atetrakis{tris(dialkylamino)phosphoranilideneamino}phosphonium cation. 3.The method as claimed in claim 1, wherein a cation forming the organicoxysalt compound is a tetraalkylammonium cation, a tetraarylphosphoniumcation, or a hexaarylphosphoranilidene animonium cation.
 4. The methodas claimed in claim 1, wherein an anion forming the organic oxysaltcompound is an organic oxyanion derived from a monohydric alcohol, anorganic oxyanion derived from a monocarboxylate, or an organic oxyanionderived from a polycarboxylate.
 5. The method as claimed in claim 1,wherein an anion forming the organic oxysalt compound is an organicoxyanion derived from a monohydric alcohol.
 6. The method as claimed inclaim 1, wherein the hydroxycarbonyl compound is an α-hydroxyketone oran α-hydroxycarboxylate.
 7. The method as claimed in claim 1, whereinthe polar unsaturated compound is a chemical compound having both apolar functional group selected from carbonyl, cyano, or pyridyl groups,and an unsaturated group in the same molecule and, in addition, thefunctional group and the unsaturated group form a directly or indirectlyconjugated system.
 8. The method as claimed in claim 1, wherein thepolar unsaturated compound is a (meth)acrylate, a (meth)acrylonitrile, a(meth)acrylamide, a vinylpyridine, a N-substituted maleimide, avinylketone, or a styrene derivative.
 9. The method as claimed in claim1, wherein the polar unsaturated compound is a monoester formed byesterification between a monohydric alcohol and acrylic acid ormethacrylic acid, a monoester formed by esterification between acrylicacid or methacrylic acid and a dihydric alcohol one end of which isprotected by ether linkage, a polyester formed by esterification betweenacrylic acid or methacrylic acid and all of the hydroxyl groups of thepolyhydric alcohol having two or more hydroxyl groups, an acrylonitrile,a methacrylonitrile, a N,N-disubstituted mono(meth)acrylamide, apyridine substituted by vinyl or isopropenyl group, a N-aromaticsubstituted maleimide or a vinylketone.
 10. The method as claimed inclaim 1, wherein an active hydrogen compound is used as a chain transferagent.
 11. The method as claimed in claim 1, wherein the reaction isconducted in presence of a chain transfer agent which is amonocarboxylate, a polycarboxylate, a monohydric alcohol, a polyhydricalcohol, a monothiol, a (co)poly(alkyleneoxide) having an activehydrogen at its end and/or in its backbone chain, a(co)poly{(meth)acrylate}, a (co)poly{(meth)acrylonitrile}, a(co)poly(acrylamide), a (co)poly(vinylpyridine), a(co)poly(N-substituted maleimide), a(co)poly(vinylketone), or a(co)poly(styrene derivative).
 12. The method as claimed in claim 1,wherein a copolymer is produced by using at least two or more of thepolar unsaturated compounds together.
 13. A thermosetting powder coatingcomposition comprising; a living polymerized (co)polymer (A) obtained bythe method as claimed in claim 1, and a curing agent compositioncomponent (B) which can cure said (co)polymer.
 14. The thermosettingpowder coating composition as claimed in claim 13, wherein the(co)polymer(A) comprises an epoxy group.
 15. The thermosetting powdercoating composition as claimed in claim 13, wherein the (co)polymer(A)has a glass transition temperature of 10° C.-100° C.
 16. Thethermosetting powder coating composition as claimed claim 13, whereinthe curing agent composition component (B) which can cure the(co)polymer comprising; (b-1) a polycarboxylic acid and/or (b-2) apolycarboxylic acid anhydride.
 17. The thermosetting powder coatingcomposition as claimed in claim 13, wherein the thermosetting powdercoating composition is for use as top coating of automobiles.